Methods and Precursors for Selective Deposition of Metal Films

ABSTRACT

Methods and precursors for selectively depositing a metal film on a silicon nitride surface relative to a silicon oxide surface are described. The substrate comprising both surfaces is exposed to a blocking compound to selectively block the silicon oxide surface. A metal film is then selectively deposited on the silicon nitride surface.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/753,534, filed Apr. 3, 2020, which is the National Stage entry ofPCT/US2018/054736, filed on Oct. 5, 2018, which claims priority to U.S.Provisional Application Ser. No. 62/569,240, filed Oct. 6, 2017, theentire disclosures of which are hereby incorporated by reference herein.

TECHNICAL FIELD

Embodiments of the disclosure relate to methods for selectivelydepositing metal films. More particularly, embodiments of the disclosureare directed to methods selectively depositing metal films on siliconnitride and not on silicon dioxide.

BACKGROUND

The semiconductor industry faces many challenges in the pursuit ofdevice miniaturization which involves rapid scaling of nanoscalefeatures. Such issues include the introduction of complex devicefabrication processes with multiple lithography steps and etch.Furthermore, the semiconductor industry would like low cost alternativesto high cost EUV for patterning complex architectures. To maintain thecadence of device miniaturization and keep chip manufacturing costsdown, selective deposition has shown promise as it has the potential toremove costly lithographic steps by simplifying integration schemes.

Selective deposition of materials can be accomplished in a variety ofways. For instance, some process may have inherent selectivity tosurfaces just based on their surface chemistry. These processes arefairly rare and usually need to have surfaces with drastically differentsurface energies, such as metals and dielectrics. In the cases wheresurfaces are similar (SiO₂ versus SiN) the surfaces need to beselectively blocked by employing surface treatments that selectivelyreact with one surface and not the other, effectively blocking anysurface reactions during a subsequent deposition process.

Selective-area atomic layer deposition (SA-ALD) can be used to depositselectively only on certain materials while not on others. In someembodiments, the surfaces on which deposition is not achieved areblocked by a chemical inhibitor or surface treatment. Yet, somedeposition precursors are not effectively blocked by currenttechnologies.

Therefore, there is an ongoing need in the art for methods and materialsto inhibit deposition on certain surfaces while selectively depositingmetal-containing films on other surfaces.

SUMMARY

One or more embodiments of the disclosure are directed to methods ofselectively depositing a metal film. The methods comprise exposing asubstrate with a first surface comprising SiO₂ and a second surfacecomprising Si_(x)N_(y) to a blocking precursor to form a blocked firstsurface. The blocking precursor comprises a compound of the formulaR₃Si—X, where each R is independently C1-C4 alkyl and X is a reactivehandle. The substrate is exposed to a metal precursor. The metalprecursor comprises a compound of the formula M(NR′₂)_(a) where each R′is independently C1-C4 alkyl and is greater than or equal to one. Thesubstrate is exposed to a reagent to react with the metal precursor toform a metal film on the second layer.

Additional embodiments of the disclosure are directed to methods ofselectively depositing a titanium nitride film. The methods compriseexposing a substrate with a first surface comprising SiO₂ and a secondsurface comprising Si_(x)N_(y) to a blocking precursor to form a blockedfirst surface. The blocking precursor comprisestrimethylsilylpyrrolidine. The substrate is exposed to a metal precursorto deposit a layer of metal species on the second surface. The metalprecursor comprises TDEAT. The substrate is exposed to ammonia to reactwith the layer of metal species on the second layer to form a titaniumnitride film.

Further embodiments of the disclosure are directed to methods ofselectively depositing a hafnium oxide film. The methods compriseexposing a substrate with a first surface comprising SiO₂ and a secondsurface comprising Si_(x)N_(y) to a blocking precursor to form a blockedfirst surface. The blocking precursor comprisestrimethylsilylpyrrolidine. The substrate is exposed to a metal precursorto deposit a layer of metal species on the second surface. The metalprecursor comprises PDMAH. The substrate is exposed to water to reactwith the layer of metal species on the second layer to form a hafniumoxide film.

BRIEF DESCRIPTION OF THE DRAWING

So that the manner in which the above recited features of the disclosurecan be understood in detail, a more particular description of thedisclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawing. Itis to be noted, however, that the appended drawing illustrates onlytypical embodiments of the disclosure and is therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments.

FIG. 1 illustrates a selective deposition process in accordance with oneor more embodiment of the disclosure; and

FIG. 2 illustrates an exemplary system for processing a substrateaccording to one or more embodiment of the disclosure.

DETAILED DESCRIPTION

Embodiments of the disclosure provide methods and materials forselectively depositing metal films on silicon nitride surfaces oversilicon oxide surfaces. The process of various embodiments uses atomiclayer deposition (ALD) to provide metal films on portions of asubstrate.

A “substrate surface”, as used herein, refers to any portion of asubstrate or portion of a material surface formed on a substrate uponwhich film processing is performed. For example, a substrate surface onwhich processing can be performed include materials such as silicon,silicon oxide, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure and/orbake the substrate surface. In addition to film processing directly onthe surface of the substrate itself, in the present invention, any ofthe film processing steps disclosed may also be performed on anunderlayer formed on the substrate as disclosed in more detail below,and the term “substrate surface” is intended to include such underlayeras the context indicates. Thus for example, where a film/layer orpartial film/layer has been deposited onto a substrate surface, theexposed surface of the newly deposited film/layer becomes the substratesurface. Substrates may have various dimensions, such as 200 mm or 300mm diameter wafers, as well as, rectangular or square panes. In someembodiments, the substrate comprises a rigid discrete material.

“Atomic layer deposition” as used herein refers to the sequentialexposure to a substrate of two or more deposition gases to deposit alayer of material on a substrate surface. As used in this specificationand the appended claims, the terms “reactive compound”, “reactive gas”,“reactive species”, “precursor”, “process gas”, :deposition gas” and thelike are used interchangeably to mean a substance with a species capableof reacting with the substrate surface or material on the substratesurface in a chemical reaction (e.g., substitution, elimination,addition, oxidation, reduction). The substrate, or portion of thesubstrate, is exposed sequentially to the two or more reactive compoundswhich are introduced into a reaction zone of a processing chamber. In atime-domain process, exposure to each reactive compound is separated bya time delay to allow each compound to react with the substrate surfaceand then be purged from the processing chamber. In a spatial process,different portions of the substrate surface, or material on thesubstrate surface, are exposed simultaneously to the two or morereactive compounds so that any given point on the substrate issubstantially not exposed to more than one reactive compoundsimultaneously. As used in this specification and the appended claims,the term “substantially” used in this respect means, as will beunderstood by those skilled in the art, that there is the possibilitythat a small portion of the substrate may be exposed to multiplereactive gases simultaneously due to diffusion, and that thesimultaneous exposure is unintended.

In one aspect of a time-domain process, a first reactive gas (i.e., afirst precursor or compound A) is pulsed into the reaction zone followedby a first time delay. Next, a second precursor or compound B is pulsedinto the reaction zone followed by a second delay. During each timedelay, a purge gas, such as argon, is introduced into the processingchamber to purge the reaction zone or otherwise remove any residualreactive compound or reaction by-products from the reaction zone.Alternatively, the purge gas may flow continuously throughout thedeposition process so that only the purge gas flows during the timedelay between pulses of reactive compounds. The reactive compounds arealternatively pulsed until a desired molecular layer or layer thicknessis formed on the substrate surface. In either scenario, the process ofpulsing compound A, purge gas, compound B and purge gas is a cycle. Acycle can start with either compound A or compound B and continue therespective order of the cycle until achieving a film with thepredetermined thickness.

In an embodiment of a spatial process, a first reactive gas and secondreactive gas are delivered simultaneously to the reaction zone but areseparated by an inert gas curtain and/or a vacuum curtain. The substrateis moved relative to the gas delivery apparatus so that any given pointon the substrate is exposed to the first reactive gas and the secondreactive gas, although not simultaneously.

One or more embodiments of the disclosure advantageously provide methodsof selectively depositing a metal film on a Si_(x)N_(y) surface withsubstantially no deposition on a silicon oxide (SiO₂) surface. In someembodiments, the selective deposition is advantageously accomplished bycombining a selective surface blocking step utilizing a blockingmolecule that selectively reacts with an SiO₂ surface to form a blockedsurface. Deposition proceeds on other substrate surfaces which remainunblocked.

A general surface mechanism of one or more embodiment of the disclosurecan be carried out to block SiO₂ surfaces and subsequently stop orminimize deposition of metal films thereon while depositing these metalfilms on Si_(x)N_(y). Without being bound by any particular theory ofoperation, it is believed that the blocking molecules described herein,when used with the metal precursors described herein prevent thereaction of the metal precursors with the SiO₂ surface.

In some embodiments, the SiO₂ surface groups can be reacted withblocking molecules that have reactivity with Si—OH and not Si—NH₂. Thesemolecules can be introduced to the substrates via vapor phase delivery,in solution form or in neat form. After selective surface blocking, ALDor CVD processes can be employed to grow metal films selectively on thesilicon nitride surface.

With reference to FIG. 1 , one or more embodiments of the disclosure aredirected to a method of selectively depositing a film. The methodcomprises providing a substrate 10 comprising a first material 20 and asecond material 30. As used in this manner, the term “providing asubstrate” means that the substrate is placed into a position (e.g.,within a processing chamber) for processing. The first material 20 has afirst surface 25 with hydroxide terminations 21. The second material 30has a second surface 35 with amine terminations 31.

In some embodiments, the first surface 25 comprises silicon oxide(SiO₂). In some embodiments, the first surface 25 consists essentiallyof silicon oxide. As used in this specification and the appended claims,a material that “consists essentially of” a stated composition meansthat greater than or equal to about 95%, 98% or 99% of the material isthe stated composition.

In some embodiments, the second surface 35 comprises Si_(x)N_(y). Insome embodiments, the second surface 35 consists essentially ofSi_(x)N_(y). As used in this regard, Si_(x)N_(y) is any suitablematerial comprising silicon and nitrogen. In some embodiments, thesecond surface 35 consists essentially of silicon and nitrogen. Ingeneral, these materials may include silicon nitrides. In someembodiments, the material of the second surface 35 is a stoichiometricsilicon nitride. In some embodiments, the ratio of silicon to nitrogenin the second surface 35 is about 3:4. In some embodiments, the ratio ofsilicon to nitrogen atoms is a non-stoichiometric ratio. In someembodiments, the ratio of silicon to nitrogen in the second surface 35is less than 3:4. In some embodiments, the ratio of silicon to nitrogenin the second surface 35 is greater than 3:4.

The substrate 10, and the first surface 25 and second surface 35, isexposed to a blocking precursor 60. The blocking precursor can be anysuitable compound that can react with the hydroxide terminated 21surface and not the amine terminated 31 surface. The blocking precursor60 reacts with the hydroxide terminated 21 surface to form a blockedfirst surface 23 on the first material 20.

In some embodiments, the blocking precursor 60 comprises a compound ofthe general formula R₃Si—X, where each R is independently an alkyl groupand X is a reactive handle. In some embodiments, each R is independentlya C1-4 alkyl group. As used in this regard C1-C4 alkyl means saturatedcarbon chains with 1-4 carbon atoms. In some embodiments, these carbonchains are linear. In some embodiments, these carbon chains arebranched. In some embodiments, each R is methyl. In some embodiments, Xis selected from halide, azide, amino, hydrazide, cyanide or isocyanategroups. In some embodiments, X comprises a primary, secondary ortertiary amine with linear C1-6 alkyl or branched C1-4 alkyl groups. Insome embodiments, X is a cyclic amine with an up to 6-membered ring. Insome embodiments, X comprises a cyclic pyrrolyl group (—N(CH₂)₄). Insome embodiments, the blocking precursor 60 comprisestrimethylsilylpyrrolidine (CH₃)₃SiN(CH₂)₄. In some embodiments, theblocking precursor 60 consists essentially of trimethylsilylpyrrolidine.As used in this manner, the term “consists essentially of” means thatthe reactive component of the blocking precursor (not including inert,diluent or carrier species) is greater than or equal to about 95%, 98%or 99% of the stated species, on a molar basis.

After formation of the blocked first surface 23, a selective deposition70 of a metal film 40 on the second material 30 can be performed. Themetal film 40 can be deposited by any suitable deposition techniqueknown to the skilled artisan. Suitable techniques include, but are notlimited to, chemical vapor deposition, atomic layer deposition orphysical vapor deposition.

The substrate 10, and the blocked first surface 23 and second surface35, is exposed to a metal precursor. In some embodiments, the metalprecursor chemisorbs onto the second surface 35 to deposit a layer ofmetal species on the second surface 35. In these embodiments, the layerof metal species on the second surface reacts with a reagent to form ametal film 40. In some embodiments, the metal precursor and the reagentare present at the same time and react to form a metal film 40 on thesecond surface 35. In some embodiments, the blocking precursor 60, themetal precursor and the reagent are each exposed to the substrate 10separately. In some embodiments, the metal precursor and the reagent areexposed to the substrate 10 simultaneously. Some embodiments deposit themetal film 40 through a time-domain ALD process. Some embodimentsdeposit the metal film 40 through a spatial ALD process.

The metal film is a general term used to described metal-containingmaterials. In some embodiments, the metal film is a pure metal film. Asused in this regard, “a pure metal film” means that metal atoms aregreater than or equal to about 98%, 99% or 99.5% of the metal film, onan atomic basis. In some embodiments, the metal film comprises otheratoms. In some embodiments, the metal film comprises one or more ofoxygen, nitrogen, carbon, silicon, boron or germanium.

The metal precursor can be any suitable compound that can react with thereagent to form a metal film 40. In some embodiments, the metalprecursor comprises a compound of the formula M(NR′₂)_(a) where each R′is independently C1-C4 alkyl and a is greater than or equal to one. Asused in this regard C1-C4 alkyl means saturated carbon chains with 1-4carbon atoms. In some embodiments, these carbon chains are linear. Insome embodiments, these carbon chains are branched. Compounds of thegeneral formula above may also contain other ligands as long as a isgreater than or equal to one. In some embodiments, the metal precursordoes not contain any metal halides. In some embodiments, the filmcomprises titanium and the metal precursor does not contain any TiCl₄.

Without being bound by theory, it is believed that the amino metalcomplexes disclosed herein are much larger than related metal halides.Accordingly, the blocking precursor 60 disclosed herein, after reactingwith the first surface 25, is effective to block the amino metalcomplexes but not the metal halides from reacting with the first surface25. In so doing, the disclosed methods provide for selective depositionon the second surface 35 which remains unblocked by the blockingprecursor 60.

Without being bound by theory, it is also believed that the amino metalcomplexes disclosed herein possess larger steric hindrances than relatedmetal halides. Therefore the amino metal complexes have a higher energybarrier when reacting with the blocked first surface 23 than whenreacting with the second surface 35. Accordingly, the reaction of themetal precursor with the second surface 35 is thermodynamicallyfavorable over reaction with the blocked first surface 23.

The metal of the metal precursor can be any suitable metal. In someembodiments, the metal of the metal precursor is selected from Ti, Zr,Hf, or Ta. In some embodiments, the metal precursor consists essentiallyof compounds which contain Ti. In some embodiments, the metal precursorconsists essentially of compounds which contain Zr. In some embodiments,the metal precursor consists essentially of compounds which contain Hf.In some embodiments, the metal precursor consists essentially ofcompounds which contain Ta.

In some embodiments, each R′ is methyl. In some embodiments, each R′ isethyl. In some embodiments, the R′ groups within a single ligand areidentical (e.g. N(CH₃)₂). In some embodiments, the R′ groups within asingle ligand are different (e.g. N(CH₃)(C₂H₅)).

In some embodiments, a is greater than or equal to 4. In someembodiments, the metal precursor consists essentially of Ti(N(CH₃)₂)₄(TDMAT). In some embodiments, the metal precursor consists essentiallyof Ti(N(C₂H₅)₂)₄ (TDEAT). In some embodiments, the metal precursorconsists essentially of Hf(N(CH₃)₂)₅ (PDMAH). As used in this manner,the term “consists essentially of” means that the reactive component ofthe metal precursor (not including inert, diluent or carrier species) isgreater than or equal to about 95%, 98% or 99% of the stated species, ona molar basis.

The reagent can be any suitable compound that can react with the metalprecursor to form a metal film 40. Suitable reactants may include, butare not limited to, hydrogen, ammonia, hydrazine, hydrazine derivativesand other co-reactants to make metal or metal nitride films. Suitablereactants may also include, but are not limited to, oxygen, ozone, waterand other oxygen based reagents to make metal or metal oxide films. Insome embodiments, plasmas of a reagent are used to form the metal film40. In some embodiments, the reagent comprises one or more of hydrogen,ammonia or water.

In some embodiments, the reagent consists essentially of ammonia and themetal film is a metal nitride film. In some embodiments, the reagentconsists essentially of water and the metal film is a metal oxide film.As used in this manner, the term “consists essentially of” means thatthe stated component of the reagent (not including inert, diluent orcarrier species) is greater than or equal to about 95%, 98% or 99% ofthe reagent, on a molar basis. As used in this regard, a metal nitridefilm is any film comprising metal and nitrogen atoms. As used in thisregard, a metal oxide film is any film comprising metal and oxygenatoms. Films which comprise atoms other than metal (e.g. metal nitridesor metal oxides) may or may not be comprised of atoms in astoichiometric ratio.

After formation of the metal film 40, the blocked first surface 23 canbe left on the first material 20 or removed. Since the blocked firstsurface 23 is basically one monolayer of material, it may not interferewith further processing, depending on the process conditions andsubsequent films being deposited. In some embodiments, the blocked firstsurface 23 is removed prior to further processing. The blocked firstsurface 23 can be removed by any suitable technique that can remove theblocked first surface 23 without substantially damaging the metal film40 deposited on the second material 30. Suitable techniques include, butare not limited to, oxidation or etching. Oxidation can be by exposureto an oxidizer (e.g., oxygen plasma, ozone, high temperature oxygenanneal, peroxide or water).

The methods described herein may be conducted at any suitabletemperature. In some embodiments, the substrate is maintained at atemperature in the range of about 150° C. to about 450° C., about 200°C. to about 400° C., about 250° C. to about 375° C., about 225° C. toabout 350° C., or about 250° C. to about 350° C. In some embodiments,the substrate is maintained at a temperature less than or equal to about450° C., less than or equal to about 400° C., less than or equal toabout 375° C., less than or equal to about 350° C., less than or equalto about 300° C., or less than or equal to about 250° C. In someembodiments, the substrate is maintained at a temperature greater thanor equal to about 150° C., greater than or equal to about 200° C.,greater than or equal to about 225° C., greater than or equal to about250° C., greater than or equal to about 300° C., or greater than orequal to about 350° C.

With reference to FIG. 2 , additional embodiments of the disclosure aredirected to processing system 900 for executing the methods describedherein. FIG. 2 illustrates a system 900 that can be used to process asubstrate according to one or more embodiment of the disclosure. Thesystem 900 can be referred to as a cluster tool. The system 900 includesa central transfer station 910 with a robot 912 therein. The robot 912is illustrated as a single blade robot; however, those skilled in theart will recognize that other robot 912 configurations are within thescope of the disclosure. The robot 912 is configured to move one or moresubstrate between chambers connected to the central transfer station910.

At least one pre-clean/buffer chamber 920 is connected to the centraltransfer station 910. The pre-clean/buffer chamber 920 can include oneor more of a heater, a radical source or plasma source. Thepre-clean/buffer chamber 920 can be used as a holding area for anindividual semiconductor substrate or for a cassette of wafers forprocessing. The pre-clean/buffer chamber 920 can perform pre-cleaningprocesses or can pre-heat the substrate for processing or can simply bea staging area for the process sequence. In some embodiments, there aretwo pre-clean/buffer chambers 920 connected to the central transferstation 910.

In the embodiment shown in FIG. 2 , the pre-clean chambers 920 can actas pass through chambers between the factory interface 905 and thecentral transfer station 910. The factory interface 905 can include oneor more robot 906 to move substrate from a cassette to thepre-clean/buffer chamber 920. The robot 912 can then move the substratefrom the pre-clean/buffer chamber 920 to other chambers within thesystem 900.

A first processing chamber 930 can be connected to the central transferstation 910. The first processing chamber 930 can be configured as ablocking layer deposition chamber and may be in fluid communication withone or more reactive gas sources to provide one or more flows ofreactive gases to the first processing chamber 930. The substrate can bemoved to and from the processing chamber 930 by the robot 912 passingthrough isolation valve 914.

Processing chamber 940 can also be connected to the central transferstation 910. In some embodiments, processing chamber 940 comprises aselective deposition chamber and is fluid communication with one or morereactive gas sources to provide flows of reactive gas to the processingchamber 940 to perform the isotropic etch process. The substrate can bemoved to and from the processing chamber 940 by robot 912 passingthrough isolation valve 914.

Processing chamber 945 can also be connected to the central transferstation 910. In some embodiments, the processing chamber 945 is the sametype of processing chamber 940 configured to perform the same process asprocessing chamber 940. This arrangement might be useful where theprocess occurring in processing chamber 940 takes much longer than theprocess in processing chamber 930.

In some embodiments, processing chamber 960 is connected to the centraltransfer station 910 and is configured to act as a blocking layerdeposition chamber. In some embodiments, the processing chamber 930 andprocessing chamber 960 can be configured to perform the depositionprocesses on two substrates at the same time and processing chamber 940and processing chamber 945 can be configured to perform the selectivedeposition processes.

In some embodiments, each of the processing chambers 930, 940, 945 and960 are configured to perform different portions of the processingmethod. For example, processing chamber 930 may be configured to performthe blocking layer deposition process, processing chamber 940 may beconfigured to perform the selective deposition process, processingchamber 945 may be configured as a metrology station or to perform afirst selective epitaxial growth process and processing chamber 960 maybe configured to perform a second epitaxial growth process. The skilledartisan will recognize that the number and arrangement of individualprocessing chambers on the tool can be varied and that the embodimentillustrated in FIG. 2 is merely representative of one possibleconfiguration.

In some embodiments, the processing system 900 includes one or moremetrology stations. For example metrology stations can be located withinpre-clean/buffer chamber 920, within the central transfer station 910 orwithin any of the individual processing chambers. The metrology stationcan be any position within the system 900 that allows for measurement ofthe substrate, typically without exposing the substrate to an oxidizingenvironment.

At least one controller 950 is coupled to one or more of the centraltransfer station 910, the pre-clean/buffer chamber 920, processingchambers 930, 940, 945, or 960. In some embodiments, there is more thanone controller 950 connected to the individual chambers or stations anda primary control processor is coupled to each of the separateprocessors to control the system 900. The controller 950 may be one ofany form of general-purpose computer processor, microcontroller,microprocessor, etc., that can be used in an industrial setting forcontrolling various chambers and sub-processors.

The at least one controller 950 can have a processor 952, a memory 954coupled to the processor 952, input/output devices 956 coupled to theprocessor 952, and support circuits 958 to communication between thedifferent electronic components. The memory 954 can include one or moreof transitory memory (e.g., random access memory) and non-transitorymemory (e.g., storage).

The memory 954, or computer-readable medium, of the processor may be oneor more of readily available memory such as random access memory (RAM),read-only memory (ROM), floppy disk, hard disk, or any other form ofdigital storage, local or remote. The memory 954 can retain aninstruction set that is operable by the processor 952 to controlparameters and components of the system 900. The support circuits 958are coupled to the processor 952 for supporting the processor in aconventional manner. Circuits may include, for example, cache, powersupplies, clock circuits, input/output circuitry, subsystems, and thelike.

Processes may generally be stored in the memory as a software routinethat, when executed by the processor, causes the process chamber toperform processes of the present disclosure. The software routine mayalso be stored and/or executed by a second processor (not shown) that isremotely located from the hardware being controlled by the processor.Some or all of the method of the present disclosure may also beperformed in hardware. As such, the process may be implemented insoftware and executed using a computer system, in hardware as, e.g., anapplication specific integrated circuit or other type of hardwareimplementation, or as a combination of software and hardware. Thesoftware routine, when executed by the processor, transforms the generalpurpose computer into a specific purpose computer (controller) thatcontrols the chamber operation such that the processes are performed.

In some embodiments, the controller 950 has one or more configurationsto execute individual processes or sub-processes to perform the method.The controller 950 can be connected to and configured to operateintermediate components to perform the functions of the methods. Forexample, the controller 950 can be connected to and configured tocontrol one or more of gas valves, actuators, motors, slit valves,vacuum control, etc.

The controller 950 of some embodiments has one or more configurationsselected from: a configuration to move a substrate on the robot betweenthe plurality of processing chambers and metrology station; aconfiguration to load and/or unload substrates from the system; aconfiguration to deposit a blocking layer on the first surface of asubstrate; and a configuration to form a metal film on the secondsurface of a substrate.

Although the disclosure herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent disclosure. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present disclosure without departing from the spiritand scope of the disclosure. Thus, it is intended that the presentdisclosure include modifications and variations that are within thescope of the appended claims and their equivalents.

What is claimed is:
 1. A method of selectively depositing a metal film,the method comprising: exposing a substrate with a first surfacecomprising SiO₂ and a second surface comprising silicon nitride to ablocking precursor to form a blocked first surface, the blockingprecursor comprising a compound of the formula R₃Si—X, where each R isindependently C1-C4 alkyl and X is a reactive handle; exposing thesubstrate to a metal precursor; and exposing the substrate to a reagentto react with the metal precursor to form a metal film on the secondsurface.
 2. The method of claim 1, wherein each exposure occursseparately.
 3. The method of claim 1, wherein each R is methyl.
 4. Themethod of claim 1, wherein X is selected from halide, azide, amino,hydrazide, cyanide or isocyanate groups.
 5. The method of claim 1,wherein X comprises a primary, secondary or tertiary amine with linearC1-6 alkyl or branched C1-4 alkyl groups.
 6. The method of claim 1,wherein X is a pyrrolyl group.
 7. The method of claim 1, wherein theblocking precursor consists essentially of trimethylsilylpyrrolidine. 8.The method of claim 1, wherein the metal precursor comprises one or moreof Ti, Zr, Hf, or Ta.
 9. The method of claim 1, wherein the metalprecursor does not contain any metal halides.
 10. The method of claim 1,wherein the reagent comprises one or more of hydrogen, ammonia or water.11. The method of claim 1, wherein the substrate is maintained at atemperature in the range of about 200° C. to about 400° C.
 12. A methodof selectively depositing a metal film, the method comprising: exposinga substrate with a first surface comprising SiO₂ and a second surfacecomprising silicon nitride to a blocking precursor to form a blockedfirst surface; exposing the substrate to a metal precursor, the metalprecursor comprising a compound of the formula M(NR′₂)_(a) where each R′is independently C1-C4 alkyl and a is greater than or equal to one; andexposing the substrate to a reagent to react with the metal precursor toform a metal film on the second surface.
 13. The method of claim 12,wherein each exposure occurs separately.
 14. The method of claim 12,wherein the metal precursor comprises one or more of Ti, Zr, Hf, or Ta.15. The method of claim 12, wherein the metal precursor does not containany metal halides.
 16. The method of claim 12, wherein each R′ ismethyl.
 17. The method of claim 12, wherein each R′ is ethyl.
 18. Themethod of claim 12, wherein a is greater than or equal to
 4. 19. Themethod of claim 12, wherein the reagent comprises one or more ofhydrogen, ammonia or water.
 20. The method of claim 12, wherein thesubstrate is maintained at a temperature in the range of about 200° C.to about 400° C.